Battery

ABSTRACT

A battery includes a positive electrode including a positive electrode active material, a negative electrode, and an electrolytic solution including a lithium hexafluorophosphate and an additive. The positive electrode active material includes a compound having a crystal structure belonging to a space group FM3-M and represented by Compositional Formula (1): Li x Me y O α F β . The additive is at least one selected from the group consisting of difluorophosphates, tetrafluoroborates, bis(oxalate)borate salts, bis(trifluoromethanesulfonyl)imide salts, and bis(fluorosulfonyl)imide salts.

BACKGROUND 1. Technical Field

The present disclosure relates to a battery.

2. Description of the Related Art

Japanese Unexamined Patent Application Publication No. 7-037617 discloses a positive electrode active material having a crystal structure belonging to a space group R3-M and represented by the formula Li_(w)M_(x)O_(y)X_(z) (where M represents Co, Ni, Mn, V, Fe, or Ti; X represents at least one halogen element; and 0.2≤w≤2.5, 0.8≤x≤1.25, 1≤y≤2, and 0<z≤1).

SUMMARY

One non-limiting and exemplary embodiment provides a battery having high reliability, which has been demanded in existing technology.

In one general aspect, the techniques disclosed here feature a battery including a positive electrode including a positive electrode active material, a negative electrode, and an electrolytic solution including lithium hexafluorophosphate and an additive. The positive electrode active material includes a compound having a crystal structure belonging to a space group FM3-M and represented by Compositional Formula (1): Li_(x)Me_(y)O_(α)F_(β), where Me represents one or more elements selected from the group consisting of Mn, Co, Ni, Fe, Al, B, Ce, Si, Zr, Nb, Pr, Ti, W, Ge, Mo, Sn, Bi, Cu, Mg, Ca, Ba, Sr, Y, Zn, Ga, Er, La, Sm, Yb, V, and Cr; and the following requirements: 1.7≤x≤2.2, 0.8≤y≤1.3, 1≤α≤2.5, and 0.5≤β≤2 are satisfied. The additive is at least one selected from the group consisting of difluorophosphates, tetrafluoroborates, bis(oxalate)borate salts, bis(trifluoromethanesulfonyl)imide salts, and bis(fluorosulfonyl)imide salts.

The present disclosure can achieve a battery having high reliability.

Additional benefits and advantages of the disclosed embodiments will become apparent from the specification and drawings. The benefits and/or advantages may be individually obtained by the various embodiments and features of the specification and drawings, which need not all be provided in order to obtain one or more of such benefits and/or advantages.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view illustrating a schematic structure of an example of the battery according to Embodiment 1;

FIG. 2 is a powder X-ray diffraction chart of the positive electrode active material of Example 1;

FIG. 3 is a cross-sectional view illustrating a schematic structure of the battery in Example 1;

FIG. 4 is a perspective view illustrating a schematic structure of the battery in Example 1;

FIG. 5 is a diagram illustrating a schematic structure of the positive electrode plate in Example 1 and a method of producing the plate;

FIG. 6 is a diagram illustrating a schematic structure of the negative electrode plate in Example 1 and a method of producing the plate; and

FIG. 7 is a perspective view illustrating a schematic structure of the battery in Example 1.

DETAILED DESCRIPTION

Embodiments of the present disclosure will now be described.

Embodiment 1

The batter according to Embodiment 1 includes a positive electrode, a negative electrode, and an electrolytic solution.

The positive electrode includes a positive electrode active material.

The electrolytic solution includes lithium hexafluorophosphate and an additive.

The positive electrode active material includes a compound having a crystal structure belonging to a space group FM3-M and represented by Compositional Formula (1): Li_(x)Me_(y)O_(α)F_(β)  (1)

In Formula (1), Me represents at least one selected from the group consisting of Mn, Co, Ni, Fe, Al, B, Ce, Si, Zr, Nb, Pr, Ti, W, Ge, Mo, Sn, Bi, Cu, Mg, Ca, Ba, Sr, Y, Zn, Ga, Er, La, Sm, Yb, V, and Cr (i.e., one or more elements selected from the group).

In Formula (1), subscripts x, y, α, and β satisfy the following requirements:

1.7≤x≤2.2,

0.8≤y≤1.3,

1≤α≤2.5, and

0.5≤β≤2.

The additive is at least one selected from the group consisting of difluorophosphates, tetrafluoroborates, bis(oxalate)borate salts, bis(trifluoromethanesulfonyl)imide salts, and bis(fluorosulfonyl)imide salts.

The structure described above prevents occurrence of oxidative degradation of PF₆ ⁻ at the interface between the electrolytic solution and the positive electrode active material represented by Compositional Formula (1). Accordingly, the reliability (e.g., discharge efficiency) of the battery can be enhanced.

Lithium hexafluorophosphate dissociates into a cation (lithium ion: Li⁺) and an anion (hexafluorophosphate ion: PF₆ ⁻) in an electrolytic solution. Accordingly, in a battery including a known positive electrode active material (e.g., active material having a layered structure defined by a space group R3-M, such as LiCoO₂ and LiMnO₂) and a known electrolytic solution, PF₆ ⁻ having a high electron density is readily oxidatively decomposed on the positive electrode. Consequently, when a large amount of Li is extracted, the reliability of the battery becomes insufficient.

In contrast, the battery including an electrolytic solution and a positive electrode active material according to Embodiment 1 can prevent occurrence of oxidative degradation of PF₆ ⁻. The factors thereof are probably as follows.

That is, the additive of the electrolytic solution according to Embodiment 1, i.e., any of difluorophosphates, tetrafluoroborates, bis(oxalate)borate salts, bis(trifluoromethanesulfonyl)imide salts, and bis(fluorosulfonyl)imide salts, dissociates in the electrolytic solution. That is, in the electrolytic solution according to Embodiment 1, the respective anions: difluorophosphate ions, tetrafluoroborate ions, bis(oxalate)borate ions, bis(trifluoromethanesulfonyl)imide ions, and bis(fluorosulfonyl)imide ions, are generated.

These anions adsorb to or are oxidatively decomposed by the positive electrode active material represented by Compositional Formula (1). Consequently, a passive layer is formed. Accordingly, the oxidative degradation of PF₆ ⁻ on the positive electrode active material is probably prevented.

The structure in Embodiment 1 can achieve a high-capacity battery.

For example, a lithium ion battery including the positive electrode active material containing the above-mentioned compound has a redox potential (Li/Li reference) of about 3.3 V and a capacity of about 220 mAh/g or more.

In the above-mentioned compound when subscript x in Compositional Formula (1) is smaller than 1.7, the usable amount of Li is small, leading to an insufficient capacity.

In the above-mentioned compound when subscript x in Compositional Formula (1) is larger than 2.2 (in other words, when subscript y is smaller than 0.8), the amount of the transition metal usable for the redox reaction is reduced. As a result, a large amount of oxygen is used in the redox reaction, leading to unstablization of the crystal structure and an insufficient capacity.

In the above-mentioned compound when subscript α in Compositional Formula (1) is smaller than 1 (in other words, when subscript β is larger than 2), the influence of F having high electronegativity is high. As a result, the electron conductivity decreases, and the capacity becomes insufficient.

In the above-mentioned compound when subscript α in Compositional Formula (1) is larger than 2.5 (in other words, when subscript β is smaller than 0.5), the influence of F having high electronegativity is low. As a result, the cation-anion interaction is reduced. Consequently, the structure is unstabilized when Li is deintercalated, and the capacity becomes insufficient.

In the positive electrode active material according to Embodiment 1, the compound represented by Compositional Formula (1) has a crystal structure belonging to a space group FM3-M (rock salt crystal structure).

In Compositional Formula (1), the ratio of Li to Me is denoted by {Li_(x)/Me_(y)}.

In {Li_(x)/Me_(y)}, subscripts x and y satisfy: 1.7≤x≤2.2 and 0.8≤y≤1.3.

Accordingly, the ratio of Li to Me is theoretically 1.31≤{Li_(x)/Me_(y)}≤2.75 and is larger than 1.

That is, the number of Li atoms for one Me atom is larger than those of known positive electrode active materials, such as LiMnO₂.

In the compound represented by Compositional Formula (1), it is conceivable that Li and Me are located at the same site.

Accordingly, the compound represented by Compositional Formula (1) can intercalate and deintercalate a larger amount of Li for one Me atom compared to known positive electrode active materials, such as LiMnO₂.

Accordingly, the positive electrode active material for a battery according to Embodiment 1 is suitable for achieving a high-capacity lithium ion battery.

In the layered structure defined by a space group R3-M, the layer structure cannot be maintained when a large amount of Li is extracted and is collapsed.

In contrast, in a rock salt crystal structure defined by the space group FM3-M as in the compound of the present disclosure, even if a large amount of Li is extracted, the structure is not collapsed and can be stably maintained. Consequently, a high-capacity battery can be achieved.

In addition, the positive electrode active material according to Embodiment 1 may mainly include the above-mentioned compound.

Such a structure can achieve a battery having a higher capacity.

Herein, the wording “mainly include” means that the positive electrode active material of Embodiment 1 includes, for example, 90 wt % or more of the above-mentioned compound.

The positive electrode active material of Embodiment 1 mainly includes the above-mentioned compound and may further include, for example, inevitable impurities or a starting material used in the synthesis of the above-mentioned compound, a byproduct, and a decomposition product.

The above-mentioned compound in the positive electrode active material according to Embodiment 1 may be a compound of Compositional Formula (1) satisfying x+y=α+β=3.

Such a structure can achieve a battery having a higher capacity.

In Embodiment 1, Me may be one element selected from Mn, Co, Ni, Fe, Al, B, Ce, Si, Zr, Nb, Pr, Ti, W, Ge, Mo, Sn, Bi, Cu, Mg, Ca, Ba, Sr, Y, Zn, Ga, Er, La, Sm, Yb, V, and Cr.

Alternatively, Me may be a solid solution of two or more elements selected from Mn, Co, Ni, Fe, Al, B, Ce, Si, Zr, Nb, Pr, Ti, W, Ge, Mo, Sn, Bi, Cu, Mg, Ca, Ba, Sr, Y, Zn, Ga, Er, La, Sm, Yb, V, and Cr.

In Embodiment 1, Me in Compositional Formula (1) may be one element selected from Mn, Co, Ni, and Fe; a solid solution composed of Ni, Co, and Mn; or a solid solution composed of Ni, Co, and Al.

Such a structure can achieve a battery having a higher capacity.

In Embodiment 1, the above-mentioned compound of Compositional Formula (1) may satisfy 1.79≤x≤2.18.

Such a structure can achieve a battery having a higher capacity.

In Embodiment 1, the above-mentioned compound of Compositional Formula (1) may satisfy 1.89≤x≤2.

Such a structure can achieve a battery having a higher capacity.

In Embodiment 1, the above-mentioned compound of Compositional Formula (1) may satisfy 0.79≤β≤1.

Such a structure can achieve a battery having a higher capacity.

In Embodiment 1, Me may contain at least one selected from the group consisting of Mn, Co, and Ni.

Such a structure can achieve a battery having a higher capacity and high reliability.

In Embodiment 1, Me may be one element selected from Mn and Co or may be a solid solution composed of Ni, Co, and Mn.

Such a structure can achieve a battery having a higher capacity and high reliability.

In Embodiment 1, the compound of Compositional Formula (1) may satisfy 1.79≤x≤2.18, 0.82≤y≤1.21, 1.5≤α≤2.5, and 0.5≤β≤1.5.

Such a structure can achieve a battery having a higher capacity and high reliability.

In Embodiment 1, the compound of Compositional Formula (1) may satisfy x=2, y=1, 1.5≤α≤2, and 1≤β≤1.5.

Such a structure can achieve a battery having a higher capacity and high reliability.

The battery in Embodiment 1 can be constituted as, for example, a lithium ion secondary battery or a nonaqueous electrolyte secondary battery.

That is, in the battery in Embodiment 1, for example, the negative electrode may include a negative electrode active material capable of occluding and releasing lithium (having characteristics of occluding and releasing lithium) or lithium metal.

FIG. 1 is a cross-sectional view illustrating a schematic structure of a battery 1000 as an example of the battery according to Embodiment 1.

As shown in FIG. 1, the battery 1000 includes a positive electrode 21, a negative electrode 22, a separator 14, a case 11, a sealing plate 15, and a gasket 18.

The separator 14 is disposed between the positive electrode 21 and the negative electrode 22.

The positive electrode 21, the negative electrode 22, and the separator 14 are impregnated with an electrolytic solution.

The positive electrode 21, the negative electrode 22, and the separator 14 form an electrode group.

The electrode group is accommodated in the case 11.

The case 11 is sealed with the gasket 18 and the sealing plate 15.

The positive electrode 21 includes a positive electrode current collector 12 and a positive electrode active material layer 13 disposed on the positive electrode current collector 12.

The positive electrode current collector 12 is made of, for example, a metal material (e.g., aluminum, stainless steel, or an aluminum alloy).

The case 11 may be used as the positive electrode current collector without disposing the positive electrode current collector 12.

The positive electrode active material layer 13 includes the positive electrode active material in Embodiment 1.

The positive electrode active material layer 13 may optionally include, for example, a conducting agent, an ion conductivity auxiliary, and a binder.

The negative electrode 22 includes a negative electrode current collector 16 and a negative electrode active material layer 17 disposed on the negative electrode current collector 16.

The negative electrode current collector 16 may be made of, for example, a metal material (e.g., copper, nickel, aluminum, stainless steel, or an aluminum alloy).

The sealing plate 15 may be used as the negative electrode current collector without disposing the negative electrode current collector 16.

The negative electrode active material layer 17 includes a negative electrode active material.

The negative electrode active material layer 17 may optionally include, for example, a conducting agent, an ion conductivity auxiliary, and a binder.

Examples of the negative electrode active material include metal materials, carbon materials, oxides, nitrides, tin compounds, and silicon compounds.

The metal material may be an elementary metal or may be an alloy.

Examples of the metal material include lithium metal and lithium alloys.

Examples of the carbon material include natural graphite, coke, carbon during graphitization, carbon fibers, spherical carbon, artificial graphite, and amorphous carbon.

From the viewpoint of capacity density, silicon (Si), tin (Sn), silicon compounds, and tin compounds can be suitably used. The silicon compounds and the tin compounds may be alloys or solid solutions.

Examples of the silicon compound include SiO_(x) (where 0.05<x<1.95). A compound (alloy or solid solution) prepared by partially replacing silicon in SiO_(x) with another element also can be used. Herein, the another element is at least one element selected from the group consisting of boron, magnesium, nickel, titanium, molybdenum, cobalt, calcium, chromium, copper, iron, manganese, niobium, tantalum, vanadium, tungsten, zinc, carbon, nitrogen, and tin.

Examples of the tin compound include Ni₂Sn₄, Mg₂Sn, SnO_(x) (where, 0<x<2), SnO₂, and SnSiO₃. These tin compounds may be used alone or in combination of two or more thereof.

The negative electrode active material may have any shape. A negative electrode active material having a known shape (such as particulate or fibrous shape) can be used.

The negative electrode active material layer 17 may be compensated (occluded) with lithium by any method. Specifically, for example, (a) lithium is deposited on the negative electrode active material layer 17 by a gas phase method, such as vacuum deposition, or (b) lithium metal foil and the negative electrode active material layer 17 are brought into contact with each other and are heated. In both methods, lithium diffuses into the negative electrode active material layer 17 by heat. In another method, lithium is electrochemically occluded in the negative electrode active material layer 17. Specifically, a battery is assembled with a lithium-free negative electrode 22 and lithium metal foil (positive electrode). Subsequently, the battery is charged such that lithium is occluded in the negative electrode 22.

Examples of the binder of the positive electrode 21 or the negative electrode 22 include poly(vinylidene fluoride), polytetrafluoroethylene, polyethylene, polypropylene, aramid resins, polyamides, polyimides, polyamideimides, polyacrylonitriles, poly(acrylic acid), poly(methyl acrylate), poly(ethyl acrylate), poly(hexyl acrylate), poly(methacrylic acid), poly(methyl methacrylate), poly(ethyl methacrylate), poly(hexyl methacrylate), poly(vinyl acetate), poly(vinyl pyrrolidone), polyethers, polyethersulfones, hexafluoropolypropylene, styrene butadiene rubber, and carboxymethyl cellulose. Alternatively, the binder may be a copolymer of two or more materials selected from the group consisting of tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ethers, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene.

Examples of the conducting agent of the positive electrode 21 or the negative electrode 22 include graphite, carbon black, conductive fibers, graphite fluoride, metal powders, conductive whiskers, conductive metal oxides, and organic conductive materials. Examples of the graphite include natural graphite and artificial graphite. Examples of the carbon black include acetylene black, Ketchen black (registered trademark), channel black, furnace black, lamp black, and thermal black. Examples of the metal powder include aluminum powder. Examples of the conductive whisker include zinc oxide whiskers and potassium titanate whiskers. Examples of the conductive metal oxide include titanium oxide. Examples of the organic conductive material include phenylene derivatives.

As the separator 14, materials having a high ion permeability and a sufficient mechanical strength can be used. Examples of such a material include porous thin film, woven fabric, and nonwoven fabric. Specifically, the separator 14 is desirably made of a polyolefin, such as polypropylene and polyethylene. A polyolefin separator 14 not only has excellent durability but also can exhibit a shutdown function when excessively heated. The separator 14 has a thickness in a range of, for example, 10 to 300 μm (or 10 to 40 μm). The separator 14 may be a monolayer film composed of one material or may be a composite film (or multilayer film) composed of two or more materials. The separator 14 has a porosity in a range of, for example, 30% to 70% (or 35% to 60%). The term “porosity” refers to the rate of the volume of holes to the total volume of the separator 14. The “porosity” is measured by, for example, a mercury press-in method.

The electrolytic solution according to Embodiment 1 includes lithium hexafluorophosphate and an additive.

The concentration of lithium hexafluorophosphate in the electrolytic solution may be 0.5 mol/L or more and 2.0 mol/L or less.

Such a structure can achieve a battery having a higher capacity and high reliability.

The concentration of the additive in the electrolytic solution may be 0.05 mol/L or more and 0.5 mol/L or less.

Such a structure can achieve a battery having a higher capacity and high reliability.

The concentration of the additive in the electrolytic solution may be 0.05 mol/L or more and 0.2 mol/L or less.

Such a structure can achieve a battery having a higher capacity and high reliability.

Examples of the additive in the electrolytic solution include difluorophosphates, tetrafluoroborates, bis(oxalate)borate salts, bis(trifluoromethanesulfonyl)imide salts, and bis(fluorosulfonyl)imide salts.

These additives may be at least one selected from the group consisting of alkali metal salts, alkaline earth metal salts, magnesium salts, aluminum salts, lithium salts, cesium salts, and calcium salts.

Such a structure can achieve a battery having a higher capacity and high reliability.

The difluorophosphate may be any salt formed of a difluorophosphate ion (PO₂F₂ ²⁻) and a cation. The cation may be a metal cation and, in particular, may be a cation of a metal element of Group 1 or 2 of the periodic table or aluminum. Examples of the difluorophosphate include LiPO₂F₂, NaPO₂F₂, CsPO₂F₂, Mg(PO₂F₂)₂, Ca(PO₂F₂)₂, and Al(PO₂F₂)₃.

The tetrafluoroborate may be any salt formed of a tetrafluoroborate ion (BF₄ ⁻) and a cation. The cation may be a metal cation and, in particular, may be a cation of a metal element of Group 1 or 2 of the periodic table or aluminum. Examples of the tetrafluoroborate include LiBF₄, NaBF₄, CsBF₄, Mg(BF₄)₂, Ca(BF₄)₂, and Al(BF₄)₃.

The bis(oxalate)borate salt may be any salt formed of a bis(oxalate)borate ion B(C₂O₄)₂ ⁻ (hereinafter, B(C₂O₄)₂ may be abbreviated as BOB) and a cation. The cation may be a metal cation and, in particular, may be a cation of a metal element of Group 1 or 2 of the periodic table or aluminum. Examples of the bis(oxalate)borate salt include LiBOB, NaBOB, CsBOB, Mg(BOB)₂, Ca(BOB)₂, and Al(BOB)₃.

The bis(trifluoromethanesulfonyl)imide salt may be any salt formed of a bis(trifluoromethanesulfonyl)imide ion (CF₃SO₂)₂N⁻ (hereinafter, (CF₃SO₂)₂N may be abbreviated as TFSI) and a cation. The cation may be a metal cation and, in particular, may be a cation of a metal element of Group 1 or 2 of the periodic table or aluminum. Examples of the bis(trifluoromethanesulfonyl)imide salt include LiTFSI, NaTFSI, CsTFSI, Mg(TFSI)₂, Ca(TFSI)₂, and Al(TFSI)₃.

The bis(fluorosulfonyl)imide salt may be any salt formed of a bis(fluorosulfonyl)imide ion (FSO₂)₂N⁻ (hereinafter, (FSO₂)₂N may be abbreviated as FSI) and a cation. The cation may be a metal cation and, in particular, may be a cation of a metal element of Group 1 or 2 of the periodic table or aluminum.

Examples of the bis(fluorosulfonyl)imide salt include LiFSI, NaFSI, CsFSI, Mg(FSI)₂, Ca(FSI)₂, and Al(FSI)₃.

The electrolytic solution according to Embodiment 1 may further include a lithium salt nonaqueous solvent.

The nonaqueous solvent in the electrolytic solution may be at least one selected from the group consisting of carbonates, carboxylates, ethers, and nitriles.

Such a structure can achieve a battery having a higher capacity and high reliability.

On this occasion, the electrolytic solution may further include fluoroethylene carbonate.

Such a structure can achieve a battery having a higher capacity and high reliability.

Examples of the nonaqueous solvent in the electrolytic solution include cyclic carbonates, linear carbonates, cyclic carboxylates, linear carboxylates, linear nitriles, cyclic ethers, and linear ethers.

The ionic conductivity of the electrolytic solution can be improved by mixing a cyclic solvent and a linear solvent at an appropriate ratio.

Use of a carbonate or a carboxylate can improve the reliability.

Examples of the cyclic carbonate include ethylene carbonate, fluoroethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, vinylethylene carbonate, and their derivatives. These cyclic carbonates may be used alone or in combination of two or more thereof.

The ionic conductivity of the electrolytic solution can be improved by using at least one selected from the group consisting of ethylene carbonate, fluoroethylene carbonate, and propylene carbonate.

The electrolytic solution including fluoroethylene carbonate can have improved stability on the negative electrode.

Examples of the linear carbonate include dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate. In these carbonates, a part of hydrogen atoms may be replaced with fluoro groups. These carbonates may be used alone or in combination of two or more thereof.

Examples of the cyclic carboxylate include γ-butyrolactone and γ-valerolactone. In these carboxylates, a part of hydrogen atoms may be replaced with fluoro groups. These carboxylates may be used alone or in combination of two or more thereof.

Examples of the linear carboxylate include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and propyl propionate. In these carboxylates, a part of hydrogen atoms may be replaced with fluoro groups. These carboxylates may be used alone or in combination of two or more thereof.

Examples of the linear nitrile include acetonitrile, propionitrile, butyronitrile, valeronitrile, isobutyronitrile, and pivalonitrile. In these nitriles, a part of hydrogen atoms may be replaced with fluoro groups. These nitriles may be used alone or in combination of two or more thereof.

Examples of the cyclic ether include 1,3-dioxolane, 1,4-dioxolane, tetrahydrofuran, and 2-methyl tetrahydrofuran. In these ethers, a part of hydrogen atoms may be replaced with fluoro groups. These ethers may be used alone or in combination of two or more thereof.

Examples of the linear ether include 1,2-dimethoxyethane, dimethyl ether, diethyl ether, dipropyl ether, ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether. In these ethers, a part of hydrogen atoms may be replaced with fluoro groups. These ethers may be used alone or in combination of two or more thereof.

The battery according to Embodiment 1 can be formed into various shapes, for example, a coin-like, cylindrical, rectangular, sheet-like, button-like, flat, or laminar battery.

Method of Producing Compound

An example of the method of producing the above-mentioned compound included in the positive electrode active material of Embodiment 1 will now be described.

The compound represented by Compositional Formula (1) can be produced by, for example, the following method.

A raw material including Li, a raw material including F, and a raw material including Me are prepared. Examples of the Li-including raw material include oxides, such as Li₂O and Li₂O₂; salts, such as LiF, Li₂CO₃, and LiOH; and lithium-transition metal composite oxides, such as LiMeO₂ and LiMe₂O₄. Examples of the F-including raw material include LiF and transition metal fluorides. Examples of the Me-including raw material include oxides in various oxidation states, such as Me₂O₃; salts, such as MeCO₃ and MeNO₃; hydroxides, such as Me(OH)₂ and MeOOH; and lithium-transition metal composite oxides, such as LiMeO₂ and LiMe₂O₄. For example, when Me is Mn, examples of the Mn-including raw material include manganese oxides in various oxidation states, such as Mn₂O₃; salts, such as MnCO₃ and MnNO₃; hydroxides, such as Mn(OH)₂ and MnOOH; and lithium-transition metal composite oxides, such as LiMnO₂ and LiMn₂O₄.

These materials are weighed so as to give a molar ratio shown by Compositional Formula (1).

On this occasion, subscripts “x, y, α, and β” in Compositional Formula (1) can be varied within the range shown by Compositional Formula (1).

The weighed raw materials are, for example, mixed by a dry process or a wet process for a mechanochemical reaction for 10 hours or more to prepare a compound represented by Compositional Formula (1). The mixing is performed with, for example, a mixer, such as a ball mill.

The compound substantially represented by Compositional Formula (1) can be prepared by adjusting the raw materials and the mixing conditions for the raw material mixture.

The use of a lithium-transition metal composite oxide as a precursor can further decrease the energy for mixing the elements. Consequently, the compound represented by Compositional Formula (1) can have a higher purity.

The composition of the resulting compound represented by Compositional Formula (1) can be determined by, for example, inductively coupled plasma (ICP) emission spectral analysis and an inert gas fusion-infrared absorption method.

The compound represented by Compositional Formula (1) can be identified by determining the space group of the crystal structure by powder X-ray analysis.

As described above, the method of producing a positive electrode active material according to an aspect of Embodiment 1 involves a step (a) of preparing raw materials and a step (b) of a mechanochemical reaction of the raw materials to prepare a positive electrode active material.

The step (a) may involve a step of mixing a raw material including Li and F and a raw material including Me at a molar ratio of Li to Me of 1.31 or more and 2.33 or less to prepare a raw material mixture.

On this occasion, the step (a) may involve a step of producing a lithium-transition metal composite oxide serving as a raw material by a known method.

The step (a) may involve a step of mixing raw materials at a molar ratio of Li to Me of 1.7 or more and 2.0 or less to prepare a raw material mixture.

The step (b) may involve a step of mechanochemically reacting raw materials with a ball mill.

As described above, the compound represented by Compositional Formula (1) can be synthesized by a mechanochemical reaction of precursors (e.g., LiF, Li₂O, oxidized transition metal, and lithium-transition metal composite) with a planetary ball mill.

On this occasion, the compound can include a larger amount of Li by adjusting the mixing ratio of the precursors.

In contrast, in a solid phase method, the precursors are decomposed into more stable compounds.

That is, the production process involving a reaction of the precursors by a solid phase method cannot produce the compound having a crystal structure belonging to a space group FM3-M and represented by Compositional Formula (1).

EXAMPLES Example 1

Synthesis of Positive Electrode Active Material

LiF and LiMnO₂ were weighed at a molar ratio LiF/LiMnO₂ of 1.0/1.0.

The resulting raw material and an appropriate amount of zirconia balls of 3 mm diameter were put in a 45-cc zirconia container, and the container was sealed in an argon glove box.

The sealed container was taken out from the argon glove box, followed by treatment with a planetary ball mill at 600 rpm for 30 hours.

The resulting compound was subjected to powder X-ray diffraction analysis.

FIG. 2 shows the results of the analysis.

The resulting compound was in a space group FM3-M.

The composition of the resulting compound was determined by ICP emission spectral analysis and an inert gas fusion-infrared absorption method.

The results demonstrated that the compound had a composition of Li₂MnO₂F.

Production of Positive Electrode Plate

Subsequently, 70 parts by mass of the resulting compound, 20 parts by mass of acetylene black, 10 parts by mass of poly(vinylidene fluoride), and an appropriate amount of N-methyl-2-pyrrolidone were mixed to prepare a positive electrode mixture slurry.

The positive electrode mixture slurry was applied to one surface of a positive electrode current collector formed of aluminum foil having a thickness of 15 μm and was then dried in vacuum at 105° C. The positive electrode mixture slurry was thus dried and rolled and formed into a 90-μm-thick positive electrode plate having a positive electrode active material layer.

Preparation of Nonaqueous Electrolytic Solution

LiPF₆ (CAS No. 21324-40-3) serving as a lithium salt was dissolved at a concentration of 1.0 mol/L in a solvent mixture (volume ratio: 20:80) of ethylene carbonate (hereinafter, referred to as EC) (CAS No. 96-49-1) and ethyl methyl carbonate (hereinafter, referred to as EMC) (CAS No. 623-53-0), and lithium difluorophosphate (LiPO₂F₂) serving as an additive was further dissolved at a concentration of 0.1 mol/L therein to prepare a nonaqueous electrolytic solution.

Formation of Sheet Battery

FIG. 3 is a cross-sectional view illustrating a schematic structure of the battery in Example 1.

FIG. 4 is a perspective view illustrating a schematic structure of the battery in Example 1.

In the sheet battery of Example 1, the electrode plate group is accommodated in an outer packaging 4. The electrode plate group includes a positive electrode 21, a negative electrode 22, and a separator 14. The positive electrode 21 is composed of a positive electrode current collector 12 and a positive electrode active material layer 13 (positive electrode mixture layer). The positive electrode active material layer 13 is disposed on the positive electrode current collector 12. The positive electrode 21 and the negative electrode 22 face each other with the separator 14 interposed therebetween to form the electrode plate group.

The positive electrode current collector 12 is connected to a positive electrode tab lead 1 c. The negative electrode 22 is connected to a negative electrode tab lead 2 c. The positive electrode tab lead 1 c and the negative electrode tab lead 2 c extend to the outside of the outer packaging 4.

A heat-bonded resin is arranged between the positive electrode tab lead 1 c and the outer packaging 4. A heat-bonded resin is arranged between the negative electrode tab lead 2 c and the outer packaging 4.

FIG. 5 is a diagram illustrating a schematic structure of the positive electrode plate in Example 1 and a method of producing the plate.

FIG. 6 is a diagram illustrating a schematic structure of the negative electrode plate in Example 1 and a method of producing the plate.

FIG. 7 is a perspective view illustrating a schematic structure of the battery in Example 1.

The positive electrode plate was processed as shown in FIG. 5. The electrode mixture area was 4 cm² as shown in FIG. 5.

The negative electrode plate was processed as shown in FIG. 6. The negative electrode used was lithium metal foil having a thickness of 300 μm.

As shown in FIG. 6, the positive electrode and the negative electrode were placed so as to face each other with a separator (polypropylene, thickness: 30 μm) therebetween. Subsequently, 120×120 mm square aluminum laminate (thickness: 100 μm) was folded, and the 120 mm edges were heat-sealed at 230° C. into a tubular form of 120×60 mm. The electrode group comprising the facing electrodes as shown in FIG. 7 was inserted into the tubular aluminum laminate from the 60 mm edge. As shown in FIG. 3, the edge of the aluminum laminate was aligned with the heat-bonded resins of the tab leads and was heat-sealed at 230° C.; 0.35 cc of a nonaqueous electrolytic solution was then poured in the tubular aluminum laminate from the edge not sealed in dry air having a dew point of −60° C., followed by being left to stand under a vacuum of 0.06 MPa for 15 minutes such that the electrolytic solution impregnated into the electrode mixture; and finally, the edge of the laminate from which the solution was poured was heat-sealed at 230° C.

As described above, a lithium secondary battery of Example 1 was produced.

Example 2

The concentration of LiPO₂F₂ as the additive was 0.05 mol/L.

A lithium secondary battery was produced as in Example 1 except for the above.

Example 3

Lithium tetrafluoroborate (LiBF₄) (CAS No. 14283-07-9) was used as the additive instead of LiPO₂F₂.

A lithium secondary battery was produced as in Example 1 except for the above.

Example 4

The concentration of LiBF₄ as the additive was 0.2 mol/L.

A lithium secondary battery was produced as in Example 3 except for the above.

Example 5

Lithium bis(oxalate)borate (hereinafter, referred to as LiBOB) (CAS No. 244761-29-3) was used as the additive instead of LiPO₂F₂.

A lithium secondary battery was produced as in Example 1 except for the above.

Example 6

Lithium bis(trifluoromethanesulfonyl)imide (hereinafter, referred to as LiTFSI) (CAS No. 90076-65-6) was used as the additive instead of LiPO₂F₂.

A lithium secondary battery was produced as in Example 1 except for the above.

Example 7

Lithium bis(fluorosulfonyl)imide (hereinafter, referred to as LiFSI) (CAS No. 171611-11-3) was used as the additive instead of LiPO₂F₂.

A lithium secondary battery was produced as in Example 1 except for the above.

Example 8

Magnesium bis(trifluoromethanesulfonyl)imide (hereinafter, referred to as Mg(TFSI)₂) was dissolved at a concentration of 0.05 mol/L as the additive instead of dissolving 0.1 mol/L of LiPO₂F₂.

A lithium secondary battery was produced as in Example 1 except for the above.

Example 9

Cesium bis(fluorosulfonyl)imide (hereinafter, referred to as CsFSI) was used as the additive instead of LiPO₂F₂.

A lithium secondary battery was produced as in Example 1 except for the above.

Example 10

Calcium bis(trifluoromethanesulfonyl)imide (hereinafter, referred to as Ca(TFSI)₂) was dissolved at a concentration of 0.05 mol/L as the additive instead of dissolving 0.1 mol/L of LiPO₂F₂.

A lithium secondary battery was produced as in Example 1 except for the above.

Example 11

As the nonaqueous solvent for the nonaqueous electrolytic solution, a solvent mixture (volume ratio: 10:10:80) of EC, fluoroethylene carbonate (hereinafter, referred to as FEC) (CAS No. 114435-02-8), and EMC was used instead of a solvent mixture of EC and EMC.

A lithium secondary battery was produced as in Example 1 except for the above.

Example 12

As the nonaqueous solvent for the nonaqueous electrolytic solution, a solvent mixture (volume ratio: 20:80) of FEC and methyl 3,3,3-trifluoropropionate (hereinafter, referred to as FMP) (CAS No. 18830-44-9) was used instead of a solvent mixture of EC and EMC.

A lithium secondary battery was produced as in Example 1 except for the above.

Example 13

As the positive electrode active material, Li₂Ni_(0.33)Co_(0.33)Mn_(0.33)O₂F having a crystal structure belonging to a space group FM3-M was used instead of Li₂MnO₂F.

A lithium secondary battery was produced as in Example 1 except for the above.

The positive electrode active material Li₂Ni_(0.33)Co_(0.33)Mn_(0.33)O₂F was synthesized by the same procedure as that of the synthesis of Li₂MnO₂F except that LiNi_(0.33)Co_(0.33)Mn_(0.332) was used as a raw material.

Example 14

As the positive electrode active material, Li₂CoO₂F having a crystal structure belonging to a space group FM3-M was used instead of Li₂MnO₂F.

A lithium secondary battery was produced as in Example 1 except for the above.

The positive electrode active material Li₂CoO₂F was synthesized by the same procedure as that of the synthesis of Li₂MnO₂F except that LiCoO₂ was used as a raw material.

Example 15

As the positive electrode active material, Li₂MnO_(1.5)F_(1.5) having a crystal structure belonging to a space group FM3-M was used instead of Li₂MnO₂F.

A lithium secondary battery was produced as in Example 1 except for the above.

The positive electrode active material Li₂MnO_(1.5)F_(1.5) was synthesized by the same procedure as that of the synthesis of Li₂MnO₂F except that Li₂O, LiF, MnO, and Mn₂O₃ were used as raw materials at a molar ratio Li₂O/LiF/MnO/Mn₂O₃ of 1/6/2/1.

Comparative Example 1

Li₂PO₂F₂ was not dissolved in the nonaqueous electrolytic solution.

A lithium secondary battery was produced as in Example 1 except for the above.

Comparative Example 2

Li₂PO₂F₂ was not dissolved in the nonaqueous electrolytic solution.

A lithium secondary battery was produced as in Example 13 except for the above.

Comparative Example 3

Li₂PO₂F₂ was not dissolved in the nonaqueous electrolytic solution.

A lithium secondary battery was produced as in Example 14 except for the above.

Comparative Example 4

Li₂PO₂F₂ was not dissolved in the nonaqueous electrolytic solution.

A lithium secondary battery was produced as in Example 15 except for the above.

Comparative Example 5

As the positive electrode active material, LiCoO₂ having a crystal structure belonging to a space group R3-M was used instead of Li₂MnO₂F. The positive electrode active material LiCoO₂ was synthesized in accordance with a known procedure.

A lithium secondary battery was produced as in Example 1 except for the above.

Evaluation of Battery

In the evaluation of the batteries produced as described above, each battery was sandwiched by stainless steel plates (thickness: 2 mm) of 80×80 cm with the laminate therebetween, and the electrode plates were applied with a pressure of 0.2 MPa by a U-shaped clamp. The evaluation was all performed in a thermostat chamber of 25° C.

Charging and discharging at a constant current of 0.1 mA were repeated two cycles such that the positive electrode is completely impregnated with the electrolytic solution. The charging and the discharging were stopped at battery voltages of 4.7 V and 1.5 V, respectively, and the battery was left to stand during the interval between the charging and the discharging for 20 minutes at an open circuit.

Subsequently, one cycle of charging and discharging was further performed under the same conditions. The discharge efficiency (the value obtained by dividing the discharge capacity by the charge capacity) of this third cycle was used as an index of reliability.

These results are shown in Table together with the results of discharge capacity per weight of the positive electrode active material.

TABLE Additive Discharge Positive electrode Nonaqueous concentration capacity Discharge active material solvent Additive (mol/L) (mAh/g) efficiency Example 1 Li₂MnO₂F EC + EMC LiPO₂F₂ 0.1 280 91% Example 2 Li₂MnO₂F EC + EMC LiPO₂F₂ 0.05 278 89% Example 3 Li₂MnO₂F EC + EMC LiBF₄ 0.1 277 89% Example 4 Li₂MnO₂F EC + EMC LiBF₄ 0.2 278 90% Example 5 Li₂MnO₂F EC + EMC LiBOB 0.1 285 93% Example 6 Li₂MnO₂F EC + EMC LiTFSI 0.1 281 92% Example 7 Li₂MnO₂F EC + EMC LiFSI 0.1 280 93% Example 8 Li₂MnO₂F EC + EMC Mg (TFSI)₂ 0.05 278 94% Example 9 Li₂MnO₂F EC + EMC CaFSI 0.1 277 92% Example 10 Li₂MnO₂F EC + EMC Ca (TFSI)₂ 0.05 278 94% Example 11 Li₂MnO₂F EC + FEC + EMC LiPO₂F₂ 0.1 281 92% Example 12 Li₂MnO₂F FEC + FMP LiPO₂F₂ 0.1 280 92% Example 13 Li₂Ni_(0.33)Co_(0.33)Mn_(0.33)O₂F EC + EMC LiPO₂F₂ 0.1 270 90% Example 14 Li₂CoO₂F EC + EMC LiPO₂F₂ 0.1 250 90% Example 15 Li₂MnO_(1.5)F_(1.5) EC + EMC LiPO₂F₂ 0.1 275 91% Comparative Li₂MnO₂F EC + EMC None — 275 87% Example 1 Comparative Li₂Ni_(0.33)Co_(0.33)Mn_(0.33)O₂F EC + EMC None — 271 85% Example 2 Comparative Li₂CoO₂F EC + EMC None — 242 85% Example 3 Comparative Li₂MnO_(1.5)F_(1.5) EC + EMC None — 273 87% Example 4 Comparative LiCoO₂ EC + EMC LiPO₂F₂ 0.1 200 89% Example 5

As shown in Table, the discharge efficiency of each battery of Examples 1 to 12 is higher than that of the battery of Comparative Example 1.

This is probably caused by that oxidative degradation of PF6⁻ is prevented in the batteries of Examples 1 to 12, compared to the battery of Comparative Example 1.

Similarly, the batteries of Examples 13 to 15 have higher discharge efficiencies compared to the batteries of Comparative Examples 2 to 4, respectively.

Furthermore, the batteries of Examples 1 to 15 have higher discharge capacities compared to that of Comparative Example 5.

The results described above demonstrate that the lithium secondary battery according to the present disclosure has a high capacity and a high discharge efficiency (reliability).

The battery of the present disclosure can be suitably used as, for example, a lithium secondary battery. 

What is claimed is:
 1. A battery comprising: a positive electrode including a positive electrode active material; a negative electrode; and an electrolytic solution including a lithium hexafluorophosphate and an additive, wherein the positive electrode active material includes a compound having a crystal structure belonging to a space group FM-3M and represented by Compositional Formula (1): Li_(x)Me_(y)O_(α)F_(β)  (1) where Me is one or more elements selected from the group consisting of Mn, Co, Ni, Fe, Al, B, Ce, Si, Zr, Nb, Pr, Ti, W, Ge, Mo, Sn, Bi, Cu, Mg, Ca, Ba, Sr, Y, Zn, Ga, Er, La, Sm, Yb, V, and Cr; and subscripts x, y, α, and β satisfy the following requirements: 1.7≤x<2, 0.8≤y≤1.3, 1≤α≤2.5, 0.5≤β≤2, and x+y=α+β=3, and the additive is at least one selected from the group consisting of difluorophosphates, tetrafluoroborates, bis(oxalate)borate salts, bis(trifluoromethanesulfonyl)imide salts, and bis(fluorosulfonyl)imide salts, and wherein the electrolytic solution includes 0.05 mol/L or more and 0.5 mol/L or less of the additive.
 2. The battery according to claim 1, wherein the electrolytic solution includes 0.05 mol/L or more and 0.2 mol/L or less of the additive.
 3. The battery according to claim 1, wherein the electrolytic solution includes 0.5 mol/L or more and 2.0 mol/L or less of lithium hexafluorophosphate.
 4. The battery according to claim 1, wherein the electrolytic solution includes a nonaqueous solvent, and the nonaqueous solvent is at least one selected from the group consisting of carbonates, carboxylates, ethers, and nitriles.
 5. The battery according to claim 4, wherein the electrolytic solution further includes fluoroethylene carbonate.
 6. The battery according to claim 1, wherein Me includes at least one selected from the group consisting of Mn, Co, and Ni.
 7. The battery according to claim 6, wherein Me is an element selected from the group consisting of Mn and Co or is a solid solution composed of Ni, Co, and Mn.
 8. The battery according to claim 1, wherein the positive electrode active material includes 90 wt % or more of the compound.
 9. The battery according to claim 1, wherein the compound satisfies: 1.79≤x<2; 0.82≤y≤1.21; 1.5≤α≤2.5; and 0.5≤β≤1.5.
 10. The battery according to claim 9, wherein the compound satisfies: x<2; y=1; 1.5≤α≤2; and 1≤β≤1.5. 